Vinylidene fluoride polymerization by metal-free selective activation of hydrogen peroxide: microstructure determination and mechanistic study

Abstract

Hydrogen peroxide-initiated radical polymerization of vinylidene fluoride (VDF) at 130 °C in dimethyl carbonate is presented.

Surfactant-free emulsion polymerization of vinylidene fluoride mediated by RAFT/MADIX reactive poly(ethylene glycol) polymer chains

“…For the sake of clarity, this structure only accounts for the normal head-to-tail additions of propagating radicals (-CH 2 CF 2 -CH 2 CF 2 -) onto VDF and not for the well-known and more complicated microstructure of PVDF produced by free radical polymerization, which additionally includes head-to-head (-CH 2 CF 2 -CF 2 CH 2 -) and tail-to-tail (-CF 2 CH 2 -CH 2 CF 2 -) additions. 1,60 Strong of these first understandings on the potential stabilization mechanisms and on the role of PEG-OH as precursor of stabilizer in VDF emulsion polymerization, we then investigated the use of PEG-X (M n = 2300 g mol -1 and Đ = 1.03) as stabilizer precursor. The choice of the installation of a xanthate moiety at the end of the PEG chains was dictated by the good control observed when RAFT polymerization of VDF was conducted in organic solvent [61][62][63][64][65][66][67][68] and by the successful block copolymer syntheses reported in organic solvent by chain extension using polymers functionalized with xanthate chain ends, [69][70][71][72] including an attempt to perform VDF PISA in dimethyl carbonate from a poly(vinyl acetate) macroCTA.…”

Poly(ether)s derived from oxa-Michael polymerization: a comprehensive review

“…The obtained polyester was further either depolymerized or used in radical copolymerization with additional vinyl monomers [60]. In addition, reports on oligomerization of 2-trifluoromethacrylic acid by oxa-Michael addition are available [39].…”

“…Only few reports on Brønsted or Lewis acid catalyzed oxa-Michael reactions are available [37][38][39], as in general deprotonation of the alcohol is crucial and activation of the Michael acceptor by Lewis acids is not sufficient. Instead, Brønsted or Lewis bases are as aforementioned commonly used as catalysts.…”

Amphiphilic block copolymers of poly(vinylidene fluoride) and poly(ethylene glycol)

“…41,42 In general, PVDF, like most fluoropolymers, is produced by free radical polymerization in emulsion, suspension, or solution with peroxide initiators. [43][44][45] The controlled radical polymerization of fluoropolymers, particularly VDF, is extremely difficult due to the high melting temperature and low solubility of PVDF in common organic solvents. 6 Tatemoto pioneered the iodine transfer polymerization (ITP) of fluoropolymers in 1979 and published a few papers in the 1980s and 1990s.…”